Manufacture of pyranthrone derivatives



Patented Dec 16, 1930 v UNITED STAT S PATENT OFFICE ARNOLD SHEPI-IERDSON -AND SIDNEY THOBNLEY, OE BLAGKLEY, MANCHESTER, ENG- LAND,ASSIGNORS 'ro- BRITISH" DYEsTUrrs CORPORATION LIMITED, F MAN.

7 f-GdnEsrEa, ENGLAND f MANUFACTURED]? PYRANTI-IRONE DERIVATIVES NoDrawing. Original application filed September 29, 1927, Serial No.222,932, and in Great Britain .0ctober'8, 1926. Divided and thisapplication filed May 9,:1929. Serial No. 361,844. r

. 1111a copendingapplication Ser. No. 217 .5410 filed byone of :us,Sidney vThornley, on May 21, 1927, 'which matured into Patent No.1,662,872 on March,20, 1928, there is dis closed the manufacture of newvat dyestuffs from flavanthrone. That application disclosesa process ofreactingiupon flavanthrone withhydroxyl amine orsalts thereof, toform anamino derivative of flavanthrone and then subsequently acylating theamino derivative thus formed by reacting the same with an acylatingagent to produce an acyl-amino-fiavanthron'e. Theseacylsamino-flavanthrones dye cotton in "brown shades in an advantageousmanner,

In our copending application Ser. No. 222,932 of which the presentapplication is A a division, we describe the manufacture of other newand useful-vat dyestuffs of a different type which may be made fromcertain pyrant-hrone compoundsj'by a somewhat sim- I ilar procedure. ourinvention as disclosed "in our copending application Ser. No. 222,932,

.1 3 ino derivatives of the same, the said amino derivatives beingsubsequently reacted with an acylating agent to convert them intocorresponding acyl-amino compounds; and it further comprises as newdyestuffs the amino and acyl amino compounds thus produced.

The parent application Ser. No. 222,932 is mainly directed to aminopyranthrones and the process of making the same. Our present applicationis mainly'directed to the acyl- 'aminocompoundsand the process ofmakingthese compounds. 0 p 7 1 ,jIn making the amino derivatives, we havefound that the reaction between the pyranthr ne -01np ad and th .hydrxyl amine may be advantageously carried out in the presence of sulphuricacid. Also the presence of ferrous sulphate during such reaction isadvantageous.

By our process, pyranthrone is easily con verted into new and useful vatdyestuffs. The halogenated pyranthrones, for instance, chloro or bromopyranthrone, are likewise converted into similar dyestuffs equally asvaluable.

'The amino compounds are useful'both as dyestuffs and as intermediates.They dye cotton from an alkaline hydrosulphite vat in deep brown shades.Again they may serve as intermediates and be themselves converted intoother dyestuffs. When treated with an acylating agent for instance,benzoyl chlo ride, acetyl chloride, etc., they are converted into thecorresponding acyl derivatives.

These acyl compounds also give various brown shades. When a benzoylgroup has brown shade is obtained on cotton;

We have lndicated the broad scope of our mventlon. Our process iscapable of various modifications. -The time, temperature and suchdetails maybe varied within certain limits. The following examples aretypical embodiments of our invention and illustrate it withoutlimitingthe scope thereof. In

.cooled, 24 parts of ferrous sulphate crystals been introduced into thecompound a reddish substance dyes cotton from a hydrosulphite" "ofExample 1', 150'parts of nitrobenzene, and

vat in deep brown shades. Treatment of the dyed fibre with cold sodiumhypochlorite solution TW.) causes a considerable change in the shade.

The product of Example 1 is probably an animated pyranthrone containingup to three amino groups and represented by the for mulain which a; isan integer probably less than a. The vat dyes produced by the presentprocess are dark colouredsubstances, insolu- .blein water but slightlysoluble in organic solvents.

A similar product is obtained when the reaction'is carried out in theabsence of ferrous sulphate;

' Ewample 2.1 0 parts of the dried product 36 parts of benzoyl'chlorideare heated with stirring at 170 C. for 1% hours.v Afterwards, thetemperature is raised to 210 C. j and maintained at 205-210 C. for 2hours.

The reaction mixture is cooled, 280 parts methylated spirits added,stirred for an hour,

. and filtered. The residue is washed with denaturated alcohol ofthe-type of methylated spirits until free from nitrobenzene and isthenboi-led with 200 parts ofwater containing 25 parts of sodiumhypochlorite-(15 per "cent available chlorine) for 30 minutes.

Thistreatment is followed by the addition of 10 parts ofglacial'aceticacid and a further heatingfor 15 minutes at a boilingtemperature. "After separation by filtration, the

residue is well washed with water and dried.

The. product is a dark "brown substance, slightly soluble in hotnitrobenzene or aniline giving orange brown solutions, insoluble inwater, soluble in concentrated sulphuric acid f to a b'lue solutionwhich reddens when heated "with a little boric acid. The product ishydrolyzed by the heating With per cent sulphuric acid giving anaminated'pyranv throne and benzoicacid. The compound gives a reddishviolet vat with alkaline hydrosulphite, from which cotton isdyed reddishbrown. The 'sh'adeis fast to chlorine.

The formula of. the benzoylated derivative is probably Y 7 wherein w isan integer probably less than 4. In place of the ibenzoyl chloride inthis example, we may use other acylatingagents such as acetic anhydride,acetyl chloride, oXalyl' chloride, .anisoyl chlorideyetc. By

I this means various shadesol brown may be;

' obtained. V The vat. dyestuflis producjedby this 'acylatingprocess aredark coloured substances, in-

soluble in waterbut slightly soluble in organic solvents. They arehydrolyzedbyheatingwith '80 per centsulphuric acid, giving 'amidated'pyranthrones'j and carboxylic acid,

RCOOH; These acyl'ated vat dyestuiis may be represented byitheprobableformula Nacoa),

wherein m is an integer-probably less than 4i and COR represents anacylradical. V VVhat we claim and desire to secure by Letters Patent is I 1.The vat dyes of formula dark coloured substances insoluble in. water andlittle soluble in organic solvents, dyeing 7 probable 1 general;

cotton in brown shades from a hydrosulphite vat, and being hydrolyzed byheating with 80per'cent sulphuricacid to an 'aminated pyanthrone and acarboxylic' atzidf-RCOOH. V

2. The vat dye of probable formula sulphuric acid, the colour becomingredder when the solution is warmed with a little boric acid, dyeingcotton reddish brown from a reddish violet hydrosulphite vat, and beinghydrolyzed by hot 80 per cent sulphuric acid with production of anaminated pyranthrone and benzoic acid.

.3. In the manufacture of acylated vat dyestuffs from amidatedpyranthrone compounds of the class consisting of pyranthrone andhalogenated pyranthrones, the process which comprises reacting anacylating agent with an amino pyranthrone compound containing less thanfour amino groups, to convert the said amino pyranthrone compound intothe corresponding acyl amino compound, the said amino pyranthronecompound being obtainable by condensing hydroxyl amine hydrochloridewith a pyranthrone compound of the class consisting of pyranthrone and Ihalogenated pyranthrone.

4. In the manufacture of benzoylated vat dyestuffs from aminopyranthrone compounds of the class consisting of pyranthrone andhalogenated pyranthrones, the process which comprises reacting abenzoylating agent with an amino pyranthrone compound containing lessthan four amino groups to convert the said amino compound into thecorresponding benzoylated amino compound, the said amino pyranthronebeing obtainable by condensing hydroxyl amine hydrochloride with apyranthrone compound of the class consisting of pyranthrone andhalogenated pyranthrones.

5. In the manufacture of acylated vat dyestuffs from amino pyranthronecompounds of the class consisting of pyranthrone and halogenatedpyranthrones, the process which comprises reactingan acylating agenthaving the probable formula n-p-cl wherein t represents an acyl. groupwith an amino pyranthrone compound having the probable formula wherein00 represents an integer probably less than 4, to convert the said aminopyranthrone into an acyl amino compound having the probable formula E 1C H .(NH.COR),

wherein m is an integer probably less than 4, to convert the said aminopyranthrone into a benzoylated amino compound having the probableformula II 0 wherein 00 represents an integer probably less than 4. a

In witness whereof we aflix our signatures.

ARNOLD SHEPHERDSON. SIDNEY THORNLEY.

